Development of Magnesium Oxide-Silver Hybrid Nanocatalysts for Synergistic Carbon Dioxide Activation to Afford Esters and Heterocycles at Ambient Pressure.

Autor: Gulati U; Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.; Department of Chemistry, University of Delhi, Delhi-110007, India., Rajesh UC; Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States., Rawat DS; Department of Chemistry, University of Delhi, Delhi-110007, India., Zaleski JM; Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
Jazyk: angličtina
Zdroj: Green chemistry : an international journal and green chemistry resource : GC [Green Chem] 2020 May 21; Vol. 22 (10), pp. 3170-3177. Date of Electronic Publication: 2020 Mar 24.
DOI: 10.1039/c9gc04040d
Abstrakt: Multi-metallic hybrid nancatalysts consisting of a porous metal oxide host and metal satellite guests serve as a scaffold for multi-step transformations of divergent and energy-challenging substrates. Here we have developed a 3D porous MgO framework (Lewis basic host) with Ag 0 nanoparticles (noble metal guest) for ambient pressure activation and insertion of CO 2 into unsaturated alkyne substrates. The hybrid MgO@Ag-x (x = 2, 5, 7, 8 at % Ag) catalysts are synthesized by impregnating Ag + ions in porous MgO cubes followed by reduction using NaBH 4 . Morphological (SEM, TEM, EDX mapping) and structural (PXRD, XPS) characterization reveal that the micron-sized hybrid cubes derive from self-assembly of ~100 nm (edge length) MgO cubes decorated with ~ 5 to 25 nm Ag 0 NPs. Detailed XPS analysis illustrates Ag 0 is present in two forms, <10 nm NPs and ~25 nm aggregates. The MgO@Ag-7 catalyst is effective for inserting CO 2 into aryl alkynes followed by S N 2 coupling with allylic chlorides to afford a wide range of ester and lactone heterocycles in excellent yields (61-93%) and with low E-factor (2.8). The proposed mechanism suggests a CO 2 capture and substrate assembly role for 3D porous MgO while Ag 0 performs the key activation of alkyne and CO 2 insertion steps. The catalyst is recyclable (5x) with no significant loss of product yield. Overall, these results demonstrate viable approaches to hybrid catalyst development for challenging conversions such as CO 2 utilization in a green and sustainable manner.
Competing Interests: Conflicts of interest The authors declare no competing financial interests.
Databáze: MEDLINE
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